Thermal methods for cleaning post-CMP wafers

ABSTRACT

Methods for cleaning semiconductor wafers following chemical mechanical polishing are provided. An exemplary method exposes a wafer to a thermal treatment in an oxidizing environment followed by a thermal treatment in a reducing environment. The thermal treatment in the oxidizing environment both removes residues and oxidizes exposed copper surfaces to form a cupric oxide layer. The thermal treatment in the reducing environment then reduces the cupric oxide to elemental copper. This leaves the exposed copper clean and in condition for further processing, such as electroless plating.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to the field of semiconductordevice fabrication and more particularly to wafer cleaning.

2. Description of the Prior Art

Semiconductor devices, including the Back-End of Line (BEoL)interconnect structures thereof, include conductive lines and otherfeatures that are formed from copper. During semiconductor devicefabrication on a wafer, the copper is typically deposited withintrenches or vias defined in a dielectric layer. The copper anddielectric layers are then planarized to provide a smooth and planarsurface on which to deposit additional layers. A common method forplanarizing is chemical mechanical planarization (CMP). CMP processestypically leave a residue on the exposed surface of the wafer that mustbe removed prior to the formation of subsequent layers.

Typical approaches to removing the CMP residue involve washing thewafer. For example, the wafer can be washed first in an acidic solutionand then in a basic solution, or first in a basic solution followed byan acidic solution. However, these methods are disadvantageous as theytend to remove copper, leaving the copper features recessed with respectto the surrounding dielectric layer. Other methods for removing the CMPresidue expose the wafer to an energetic plasma to etch away theresidue.

What is provided by the present invention are novel methods for removingCMP residue that do not harm either the exposed copper or the dielectriclayer.

SUMMARY

An exemplary post-CMP cleaning method comprises treating a wafer in agas-phase oxidizing environment at a temperature above about 100° C.,then treating the wafer in a gas-phase reducing environment at atemperature above about 100° C. Treating the wafer in the oxidizingenvironment can include treating the wafer in an atmosphere comprisingO₂ or O₃ while treating the wafer in the reducing environment caninclude treating the wafer in an atmosphere comprising H₂. The methodcan further comprise treating the wafer with a basic solution prior totreating the wafer in the oxidizing environment. The basic solution canhave a pH in the range of about 8 to about 11, for example, and in someembodiments comprises tetramethyl ammonium hydroxide.

The present invention also provides a method for cleaning a post-CMPwafer that includes a conductive feature having a Cu₂O surface layer.This exemplary method comprises oxidizing the Cu₂O surface layer in afirst gas-phase environment to form a CuO surface layer, then reducingthe CuO surface layer in a second gas-phase environment to elemental Cu.Oxidizing the Cu₂O surface layer can comprise treating the wafer in anatmosphere including O₂ or O₃ at a temperature above about 100° C.,while reducing the CuO surface layer can comprise treating the wafer inan atmosphere including H₂ at a temperature above about 100° C. Themethod can further comprise substantially removing a residue layer witha basic solution prior to oxidizing the Cu₂O surface layer.

Another method of the invention is directed to selectively forming acapping layer over a conductive feature of a wafer. This exemplarymethod comprises cleaning the wafer and forming the capping layerselectively over the conductive feature by electroless deposition. Inthis method, cleaning the wafer can include oxidizing a Cu₂O surfacelayer of the conductive feature in a first gas-phase environment to forma CuO surface layer, then reducing the CuO surface layer in a secondgas-phase environment to elemental Cu. In some embodiments, the cappinglayer comprises cobalt or a cobalt alloy.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a cross-section view of a post-CMP wafer including aconductive feature disposed within a dielectric layer.

FIG. 2 is a cross-section view of the top portion of the conductivefeature of FIG. 1.

FIG. 3 is a flow-chart representation of a method for cleaning thepost-CMP wafer of FIG. 1 according to an embodiment of the presentinvention.

FIG. 4 is a cross-section view of the top portion of the conductivefeature shown in FIG. 2 following treatment in an oxidizing environmentaccording to an embodiment of the present invention.

FIG. 5 is a cross-section view of the top portion of the conductivefeature shown in FIG. 3 following treatment in a reducing environmentaccording to an embodiment of the present invention.

FIG. 6 is a cross-section view of a wafer including a capping layerselectively disposed on a conductive feature according to an embodimentof the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides methods for cleaning semiconductor wafersfollowing chemical mechanical polishing. An exemplary method exposes awafer to a thermal treatment in an oxidizing environment followed by athermal treatment in a reducing environment. The thermal treatment inthe oxidizing environment both removes residues and oxidizes exposedcopper surfaces to form a cupric oxide layer. The thermal treatment inthe reducing environment then reduces the cupric oxide to elementalcopper. This leaves the exposed copper clean and in condition forfurther processing, such as electroless plating.

FIG. 1 is a cross-sectional view of a wafer 100 following a chemicalmechanical polishing (CMP) process. The wafer 100 comprises a dielectriclayer 110 and an exposed conductive feature 120 disposed within thedielectric layer 110. FIG. 1 also shows a residue layer 130 left by theCMP process on the surfaces of the dielectric layer 110 and theconductive feature 120. The residue layer 130 can include, for example,cleaning residues and corrosion inhibitors, which are typicallycopper-organic complexes. The residue layer 130 should be removed ascompletely as possible prior to further processing, such as electrolessdeposition on the conductive feature 120.

The dielectric layer 110 can comprise SiO₂ or a low dielectric constant(“low-k”) material that has a dielectric constant less than that ofSiO₂. Such low-k materials, especially those with dielectric constantslower than 3, are increasingly favored in semiconductor devicefabrication as they impart superior electrical properties to thefinished devices. Examples of suitable low-k materials includefluorosilicate glass (FSG), organosilicate glass (OSG), and highlyporous SiO₂.

The conductive feature 120 can be a conductive line or via made ofcopper, for example. Although only one conductive feature 120 is shownin FIG. 1, the conductive feature 120 is used to represent the largenumber of conductive features that are typically present on a wafer 100.

FIG. 2 shows an enlarged view of a top portion of the conductive feature120 in FIG. 1. The residue layer 130 has been omitted from FIG. 2 forclarity. As shown in FIG. 2, when the conductive feature 120 comprisescopper, the CMP process leaves the conductive feature 120 with a thinsurface layer 200 of cuprous oxide (Cu₂O).

FIG. 3 is a flow-chart representation of an exemplary method 300 forcleaning the wafer 100 to remove the residue layer 130. The methodcomprises optionally treating 310 the wafer 100 with a basic solution,treating 320 the wafer in a gas-phase oxidizing environment, andtreating 330 the wafer in a gas-phase reducing environment. Here,“gas-phase” indicates that the phase of matter within the environment isa gas, as opposed to a plasma.

The method 300 optionally begins by treating 310 the wafer 100 with abasic solution. In some embodiments, the basic solution has a pH of 10;a suitable pH range for the basic solution is about 8 to about 11. Anexemplary basic solution comprises tetramethyl ammonium hydroxide. Asuitable dwell time in the basic solution under these conditions isabout 30 seconds to about 2 minutes. Treating 310 the wafer 100 with thebasic solution serves to remove a substantial portion of the residuelayer 130 from the surface of the dielectric layer 110 and the surfaceof the conductive feature 120. In some embodiments, the treatment 310leaves approximately a monolayer of the residue layer 130 on both thesurface of the dielectric layer 110 and the surface of the conductivefeature 120. Treating 310 with the basic solution does not meaningfullyalter the Cu₂O surface layer 200 (FIG. 2).

Next, the wafer 100 is treated 320 in an oxidizing environment. Astreating 310 the wafer 100 with the basic solution is optional, in someembodiments the method 300 begins with treating 320 in the oxidizingenvironment. An exemplary oxidizing environment comprises an atmosphereincluding about 1% to about 10% molecular oxygen (O₂), or about 1% toabout 2% ozone (O₃), with the balance of the atmosphere being an inertgas such as nitrogen, helium, or argon. All percentages used herein arevolume percents unless noted otherwise.

A suitable temperature range for the oxidizing environment is about 100°C. to about 400° C. A more preferable temperature is in the range ofabout 150° C. to about 250° C. The pressure within the oxidizingenvironment can be at or below normal atmospheric pressure. An exemplarypressure is about 1 Torr. A suitable dwell time in the oxidizingenvironment under these conditions is about 2 minutes, but can be in therange of about 1 minute to about 5 minutes. Omitting the optionaltreating 310 the wafer 100 with the basic solution generally results inlonger dwell times.

Treating 320 in the oxidizing environment serves to decompose andvolatilize the organic materials in the residue layer 130. The elevatedtemperature of the oxidizing environment also serves to desorb water inthe residue layer 130. Additionally, the oxidizing environment serves tooxidize the Cu₂O surface layer 200 of the conductive feature 120. Asshown in FIG. 4, the Cu₂O surface layer 200 (FIG. 2) is oxidized to forma cupric oxide (CuO) surface layer 400.

Next, the wafer 100 is treated 330 in a reducing environment. Anexemplary reducing environment comprises an atmosphere includingmolecular hydrogen (H₂). The atmosphere can be essentially entirelyhydrogen, or can comprise a mixture of hydrogen with an inert gas suchas nitrogen, helium, or argon. The pressure within the reducingenvironment can be at or below normal atmospheric pressure. At normalatmospheric pressure, a suitable concentration of hydrogen is about 4%.At lower pressures, such as in the range of about 1 Torr to about 10Torr, the atmosphere can be entirely hydrogen. A suitable temperaturerange for the reducing environment is about 100° C. to about 400° C. Amore preferable temperature is in the range of about 150° C. to about250° C. In some embodiments, the same temperature is maintained throughboth treatments 320 and 330. A suitable dwell time in the reducingenvironment under these conditions is about 1 minute to about 2 minutes.

As shown in FIG. 5, treating 330 in the reducing environment serves toreduce the CuO surface layer 400 (FIG. 4) to a surface layer 500 ofelemental copper (Cu). Following treating 330 in the reducingenvironment, the wafer 100 can be further processed, for example, byselective electroless plating of a capping layer on the conductivefeature 120. Methods for electroless plating of cobalt and cobalt alloysare taught, for example in U.S. patent application Ser. No. 11/644,697filed on Dec. 22, 2006 and entitled “Electroless Deposition of CobaltAlloys,” and U.S. patent application Ser. No. 11/513,634 filed on Aug.30, 2006 and entitled “Processes and Systems for Engineering a CopperSurface for Selective Metal Deposition” each of which is incorporatedherein by reference. FIG. 6 shows the wafer 100 after a capping layer600 has been selectively formed on the conductive feature 120 byelectroless plating. Advantageously, the elemental copper surface layer500 provides a superior surface for the nucleation and growth of cobaltand cobalt alloy capping layers than the Cu₂O surface layer 200.

In the foregoing specification, the invention is described withreference to specific embodiments thereof, but those skilled in the artwill recognize that the invention is not limited thereto. Variousfeatures and aspects of the above-described invention may be usedindividually or jointly. Further, the invention can be utilized in anynumber of environments and applications beyond those described hereinwithout departing from the broader spirit and scope of thespecification. The specification and drawings are, accordingly, to beregarded as illustrative rather than restrictive.

1. A post-CMP cleaning method comprising: treating a wafer in agas-phase oxidizing environment at a temperature above about 100° C.;then treating the wafer in a gas-phase reducing environment at atemperature above about 100° C.
 2. The method of claim 1 whereintreating the wafer in the oxidizing environment includes treating thewafer in an atmosphere comprising O₂.
 3. The method of claim 2 whereinthe atmosphere comprises between about 1% to about 10% O₂.
 4. The methodof claim 1 wherein treating the wafer in the oxidizing environmentincludes treating the wafer in an atmosphere comprising O₃.
 5. Themethod of claim 4 wherein the atmosphere comprises between about 1% toabout 2% O₃.
 6. The method of claim 1 wherein the temperature of theoxidizing environment is between about 150° C. to about 250° C.
 7. Themethod of claim 1 wherein a pressure within the oxidizing environment isabout 1 Torr.
 8. The method of claim 1 wherein treating the wafer in theoxidizing environment includes holding the wafer in the oxidizingenvironment for a dwell time of between about 1 minute to about 5minutes.
 9. The method of claim 1 wherein treating the wafer in thereducing environment includes treating the wafer in an atmospherecomprising H₂.
 10. The method of claim 9 wherein the atmospherecomprises a mixture of H₂ and an inert gas.
 11. The method of claim 1wherein a pressure within the reducing environment is between about 1Torr to about 10 Torr.
 12. The method of claim 1 wherein the temperatureof the reducing environment is between about 150° C. to about 250° C.13. The method of claim 1 wherein a temperature of the oxidizingenvironment and a temperature reducing environment are the same.
 14. Themethod of claim 1 wherein treating the wafer in the reducing environmentincludes holding the wafer in the reducing environment for a dwell timeof between about 1 minute to about 2 minutes.
 15. The method of claim 1further comprising treating the wafer with a basic solution prior totreating the wafer in the oxidizing environment.
 16. The method of claim15 wherein the basic solution has a pH in the range of about 8 to about11.
 17. The method of claim 15 wherein the basic solution comprisestetramethyl ammonium hydroxide.
 18. The method of claim 15 whereintreating the wafer in the basic solution includes holding the wafer inthe basic solution for a dwell time of between about 30 seconds to about2 minutes.
 19. A method for cleaning a post-CMP wafer including aconductive feature having a Cu₂O surface layer, the method comprising:oxidizing the Cu₂O surface layer in a first gas-phase environment toform a CuO surface layer; then reducing the CuO surface layer in asecond gas-phase environment to elemental Cu.
 20. The method of claim 19wherein the first gas-phase environment comprises an atmosphereincluding O₂ at a temperature above about 100° C.
 21. The method ofclaim 19 wherein the first gas-phase environment comprises an atmosphereincluding O₃ at a temperature above about 100° C.
 22. The method ofclaim 19 wherein the second gas-phase environment comprises anatmosphere including H₂ at a temperature above about 100° C.
 23. Themethod of claim 19 further comprising substantially removing a residuelayer with a basic solution prior to oxidizing the Cu₂O surface layer.24. The method of claim 23 wherein the basic solution has a pH in therange of about 8 to about
 11. 25. The method of claim 23 wherein thebasic solution comprises tetramethyl ammonium hydroxide.